EP3178860A1 - Dispersions de polyuréthane séchant par oxydation ayant une résistance particulièrement élevée aux produits chimiques - Google Patents

Dispersions de polyuréthane séchant par oxydation ayant une résistance particulièrement élevée aux produits chimiques Download PDF

Info

Publication number
EP3178860A1
EP3178860A1 EP15199189.0A EP15199189A EP3178860A1 EP 3178860 A1 EP3178860 A1 EP 3178860A1 EP 15199189 A EP15199189 A EP 15199189A EP 3178860 A1 EP3178860 A1 EP 3178860A1
Authority
EP
European Patent Office
Prior art keywords
component
polyurethane
weight
acid
dispersion
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP15199189.0A
Other languages
German (de)
English (en)
Other versions
EP3178860B1 (fr
Inventor
Michael Ludewig
Maria Almato
Pantea Nazaran
Eva TEJADA
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Covestro Deutschland AG
Original Assignee
Covestro Deutschland AG
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Covestro Deutschland AG filed Critical Covestro Deutschland AG
Priority to ES15199189T priority Critical patent/ES2706826T3/es
Priority to EP15199189.0A priority patent/EP3178860B1/fr
Priority to US15/370,066 priority patent/US10640604B2/en
Priority to CN201611273031.XA priority patent/CN106866931A/zh
Publication of EP3178860A1 publication Critical patent/EP3178860A1/fr
Application granted granted Critical
Publication of EP3178860B1 publication Critical patent/EP3178860B1/fr
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/67—Unsaturated compounds having active hydrogen
    • C08G18/675—Low-molecular-weight compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/0804—Manufacture of polymers containing ionic or ionogenic groups
    • C08G18/0819—Manufacture of polymers containing ionic or ionogenic groups containing anionic or anionogenic groups
    • C08G18/0823—Manufacture of polymers containing ionic or ionogenic groups containing anionic or anionogenic groups containing carboxylate salt groups or groups forming them
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
    • C08G18/12—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step using two or more compounds having active hydrogen in the first polymerisation step
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/16—Catalysts
    • C08G18/22—Catalysts containing metal compounds
    • C08G18/24—Catalysts containing metal compounds of tin
    • C08G18/244—Catalysts containing metal compounds of tin tin salts of carboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
    • C08G18/3203—Polyhydroxy compounds
    • C08G18/3212—Polyhydroxy compounds containing cycloaliphatic groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
    • C08G18/3225—Polyamines
    • C08G18/3228—Polyamines acyclic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
    • C08G18/3225—Polyamines
    • C08G18/3234—Polyamines cycloaliphatic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/34—Carboxylic acids; Esters thereof with monohydroxyl compounds
    • C08G18/348—Hydroxycarboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/36—Hydroxylated esters of higher fatty acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
    • C08G18/758—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing two or more cycloaliphatic rings
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04—Polyurethanes
    • C09D175/14—Polyurethanes having carbon-to-carbon unsaturated bonds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09F—NATURAL RESINS; FRENCH POLISH; DRYING-OILS; DRIERS (SICCATIVES); TURPENTINE
    • C09F9/00—Compounds to be used as driers (siccatives)

Definitions

  • the present invention relates to hydrophilicized polyurethanes having a particularly high content of hydroxy-functional, unsaturated triglycerides, a process for the preparation of polyurethane dispersions based thereon, the use of the dispersions as binders in oxidatively drying paints having particularly high resistance to chemicals, as well as articles and substrates comprising these paints are coated.
  • Aqueous coating agents are now established as a substitute for solvent-based systems.
  • An important class of aqueous binders are the polyurethane dispersions ( D.Dieterich, Prog. Org. Coatings 9, 281 (1981 )), which combine the most important properties of resistance to chemicals and mechanical stress. Especially in the field of coating mechanically stressed surfaces, the use of polyurethane dispersions is therefore advantageous.
  • UV-crosslinkable polyurethane dispersions which also excellent properties can be achieved.
  • binders generally contain activated double bonds, such as, for example, acrylate groups ( EP-B-0753531 ) and are mainly established in the industrial coating of flat substrates. However, it is not practicable in all applications to crosslink with actinic radiation after the application.
  • An improvement in abrasion resistance can be achieved by systems based on modified, OH-functional triglycerides.
  • Such an aqueous polyurethane binder is used in the EP-B-0709414 described. This dehydrated castor oil is used. By dehydration OH groups of ricinoleic acid are converted into double bonds, so that the sum of the OH groups and double bonds always remains the same.
  • the object of the present invention was therefore to provide polyurethanes for use in oxidatively drying polyurethane dispersions which have a markedly increased resistance to chemicals, without losing the very good mechanical properties.
  • the polyurethane A) consists of the structural components A1) to A7).
  • the sum of all components based on the total amount of the structural components A1) to A7) is 100%.
  • OH-functional triglycerides A1) which are suitable according to the invention are triple esters of glycerol with identical or preferably different fatty acids which at least partially also have OH groups.
  • ricinoleic acid is suitable as fatty acid carrying OH groups, but it is also conceivable to introduce OH groups into the triglyceride by chemical modification of other fatty acids.
  • OH-functional fatty acids may also be present in the triglyceride A1). Both fatty acids of medium length (6 to 12 carbon atoms) and fatty acids of long length (14 to 24 carbon atoms) are suitable. Suitable fatty acids also preferably contain one or more double bonds in order to ensure the oxidative drying of the polyurethane binder. Examples of fatty acids having a double bond are undecylenic acid, myristoleic acid, palmitoleic acid, petroselinic acid, oleic acid, elaidic acid, vaccenic acid, gadoleic acid, icosenic acid, cetoleic acid, erucic acid or nervonic acid.
  • fatty acids with two or more double bonds examples include linoleic acid, alpha-linolenic acid, gamma-linolenic acid, calendic acid, punicic acid, alpha-elaeostearic acid, beta-elaeostearic acid, Arachidonic acid, timnodonic acid, clupanodonic acid, cervonic acid. Lesser amounts may also contain saturated fatty acids, such as lauric acid, myristic acid, palmitic acid, stearic acid, arachic acid, behenic acid, lignoceric acid.
  • the triglycerides which can be used according to the invention preferably also comprise one or more non-OH-functional fatty acids, such as dehydrated ricinoleic acid, oleic acid, linoleic acid, linolenic acid and, in smaller amounts, palmitic acid and / or stearic acid.
  • non-OH-functional fatty acids such as dehydrated ricinoleic acid, oleic acid, linoleic acid, linolenic acid and, in smaller amounts, palmitic acid and / or stearic acid.
  • the exact composition results from the natural composition of the vegetable oils used.
  • castor oil according to the invention As component A1, it is possible to use castor oil according to the invention as component A1). However, with natural castor oil the OH functionality is too high and the oxidative drying is not sufficient. Therefore, various methods have been proposed, on the one hand to reduce the OH functionality and on the other hand to increase the iodine value (double bond density).
  • transesterification of a mixture of castor oil with another oil having an iodine value greater than 50, preferably greater than 75 and particularly preferably greater than 100, as in the EP 1198487 is described.
  • the OH-functional triglyceride is prepared by transesterification of castor oil with soybean oil.
  • isocyanate component A2) 4,4'-diisocyanato-dicyclohexylmethane is used. It is also possible to use small amounts (up to 10% by weight, based on component A2) of other aliphatic diisocyanates.
  • Examples of other aliphatic diisocyanates are 1,6-hexamethylene diisocyanate, 1-isocyanato-3,3,5-trimethyl-5-isocyanatomethylcyclohexane (1-isocyanato-3,3,5-trimethyl-5-isocyanomethylcyclohexane or IPDI), 1 , 3-bis (isocyanato-methyl) benzene (XDI), 1,3-bis (1-isocyanato-1-methylethyl) -benzene (TMXDI), 1,5, pentamethylene diisocyanate (PDI).
  • XDI isocyanato-methyl-5-isocyanatomethylcyclohexane
  • TXDI 1,3-bis (1-isocyanato-1-methylethyl) -benzene
  • PDI pentamethylene diisocyanate
  • the low molecular weight, cycloaliphatic diols A3) are used in the construction of the prepolymer.
  • the low molecular weight, cycloaliphatic diols have a molecular weight of less than 500 g / mol, more preferably one of less than 200 g / mol.
  • Preferred cycloaliphatic diols are selected from the group consisting of 1,4-cyclohexanediol, 1,2-cyclohexanediol, 1,3-cyclohexanediol, 1,4-cyclohexanedimethanol, 1,2-cyclohexanedimethanol, 1,4-cyclohexenedimethanol, tricyclo [5.2. 1.0] decanedimethanol, tricyclo [5.2.1.0] decanediol, hydrogenated bisphenol A (2,2-bis (4-hydroxycyclohexyl) propane), and isosorbide. Particularly preferred is the use of 1,4-cyclohexanedimethanol.
  • Component A4) comprises compounds having at least one isocyanate-reactive group and additionally at least one ionic and / or potentially ionic group. It has a hydrophilic effect on the polyurethane (meth) acrylates according to the invention.
  • Hydrophilizing groups include ionic groups A41) and / or ionic groups derived from potentially ionic groups A42) (for example, by salt formation), anionic in nature such as carboxylate, sulfonate or phosphonate groups or cationic nature such as ammonium groups and / or potentially ionic groups A42), ie Groups that can be converted, for example, by salt formation into ionic groups A41). They are incorporated into the macromolecules by isocyanate-reactive groups. Preferred isocyanate-reactive groups are hydroxyl and amino groups.
  • Compounds containing potentially ionic groups A42 include compounds having potentially anionic groups such as mono- and dihydroxycarboxylic acids, mono- and diaminocarboxylic acids, mono- and dihydroxysulfonic acids, mono- and diaminosulfonic acids, mono- and dihydroxyphosphonic acids, mono- and diaminophosphonic acids and / or compounds having potential cationic groups such as ethanolamine, diethanolamine, triethanolamine, 2-propanolamine, dipropanolamine, tripropanolamine, N-methylethanolamine, N-methyl-diethanolamine and N, N-dimethylethanolamine.
  • potentially anionic groups such as mono- and dihydroxycarboxylic acids, mono- and diaminocarboxylic acids, mono- and dihydroxysulfonic acids, mono- and diaminosulfonic acids, mono- and dihydroxyphosphonic acids, mono- and diaminophosphonic acids and / or compounds having potential cationic groups such as ethanolamine, diethanolamine, triethanolamine
  • Preferred compounds contain potentially anionic groups A42) and are selected from the group consisting of dimethylolpropionic acid, dimethylolbutyric acid, hydroxypivalic acid, N- (2-aminoethyl) -alanine, 2- (2-amino-ethylamino) -ethanesulfonic acid, ethylenediamine-propyl or butylsulfonic acid, 1,2- or 1,3-propylenediamine ethylsulfonic acid, 3- (cyclohexylamino) propane-1-sulfonic acid, malic acid, citric acid, glycolic acid, lactic acid, glycine, alanine, taurine, lysine, 3,5-diaminobenzoic acid, the addition products of acrylic acid to diamines in the ratio 1: 1, such as.
  • Particularly preferred compounds containing potentially ionic groups A42) are dimethylolpropionic acid, dimethylolbutyric acid and hydroxypivalic acid. Very particular preference is given to the use of dimethylolpropionic acid
  • the acids mentioned under component A42) are converted by reaction with neutralizing agents, such as.
  • neutralizing agents such as.
  • triethylamine, ethyldiisopropylamine, dimethylcyclohexylamine, dimethylethanolamine, ammonia, N-ethylmorpholine, LiOH, NaOH and / or KOH (component A6) are converted into the corresponding salts.
  • the degree of neutralization is preferably between 50 and 125%, more preferably between 60 and 100%.
  • the degree of neutralization is defined as follows: in the case of acid-functionalized polymers, the quotient of base and acid; in the case of base-functionalized polymers as quotient of acid and base.
  • the neutralization of component A42) is preferably carried out by LiOH, NaOH, KOH, triethyleneamine or ethyldiisopropylamine, more preferably by triethyleneamine or ethyldiisopropylamine and most preferably by ethyldiisopropylamine.
  • amine-free operation it is particularly preferred to neutralize with LiOH, NaOH or KOH.
  • the compounds listed under component A4) can also be used in mixtures.
  • mono- and diamines and / or mono- or difunctional amino alcohols are used as component A5) alone or in a mixture.
  • Preferred diamines are those which are more reactive towards the isocyanate groups than water, since the extension of the polyester urethane (meth) acrylate optionally takes place in an aqueous medium.
  • the diamines are selected from the group consisting of ethylenediamine, 1,6-hexamethylenediamine, isophoronediamine, 1,3-phenylenediamine, 1,4-phenylenediamine, piperazine, 4,4'-diphenylmethanediamine, amino-functional polyethylene oxides, aminofunctional polypropylene oxides (known under US Pat name Jeffamine ® D series (Huntsman Corp. Europe, Zavantem, Belgium) and hydrazine. Very particular preference is given to isophoronediamine and ethylenediamine, and particular preference is given to the mixture of isophoronediamine and ethylenediamine.
  • catalysts component A7
  • urethanization catalysts known to those skilled in the art, such as e.g. tertiary amines or Lewis acids in question.
  • organotin compounds e.g. Dibutyltin diacetate, dibutyltin dilaurate, dibutyltin bis-acetoacetonate, tin salts such as.
  • Stannous octoate or zinc compounds e.g. Zinc acetylacetonate or zinc octoate.
  • Lewis acidic metal compounds containing molybdenum, vanadium, zirconium, cesium, bismuth or tungsten such as e.g. Bismuth octoate or zirconium octoate.
  • a catalyst which is not an organometallic compound, ie contains no covalent metal-carbon bonds Preference is given to using tin octoate or bismuth octoate.
  • Component A1) is preferred in amounts of from 40 to 60% by weight, preferably from 42 to 55% by weight, particularly preferably from 45 to 50% by weight, of component A2) in amounts of from 30 to 55% by weight from 33 to 50 wt .-%, particularly preferably from 35 to 42 wt .-%, component A3) in amounts of from 3 to 15 wt .-%, preferably from 4 to 10 wt .-%, particularly preferably from 5 to 8 Wt .-%, component A4) in amounts of 1 to 20 wt .-%, preferably from 1.5 to 15 wt .-%, most preferably from 2 to 8 wt .-%, component A5) in amounts of 1 to 20 wt .-%, preferably from 1.5 to 15 wt .-%, particularly preferably from 2 to 10 wt .-%, component A6) in amounts of 0 to 10 wt .-%, preferably from 1 to 5 wt .-%, most preferably from 1.5 to
  • Another object of the invention is a process for the preparation of polyurethane dispersions, characterized in that in a first step by reacting the components A1) to A4) optionally in the presence of a catalyst A7) and optionally in a solvent in one or more reaction steps Polyurethane prepolymer is obtained, wherein a neutralizing agent A6) can be added to produce the ionic groups necessary for the dispersion before, during or after the preparation of the addition product of A1) to A4), followed by a dispersing step by adding water to the addition product of A1) to A4) or conversion of the addition product of A1) to A4) in an aqueous template, wherein before, during or after the dispersion Chain extension by means of component A5) takes place and optionally followed by a third step in which the dispersion is freed from the organic solvent by distillation.
  • the invention therefore also provides dispersions prepared by the above process which have a solids content of 25-60%, preferably 30-50% and particularly preferably 35-45% and an average particle size of 20 to 300 nm from 30 to 200 nm.
  • the reaction of the isocyanate-containing components A2) with the isocyanate-reactive components A1), A3) and A4) takes place in a urethanization reaction which is known per se to the person skilled in the art, if appropriate with the aid of a catalyst A7.
  • the reaction is carried out at temperatures of 25 to 100 ° C, preferably 40 to 80 ° C over a period of 2 to 30 hours, preferably 4 to 15 hours.
  • suitable measuring devices installed in the reaction vessel and / or by analyzes on samples taken. Suitable methods are known to the person skilled in the art. These are, for example, viscosity measurements, measurements of the NCO content, measurement of the refractive index, measurement of the OH content, gas chromatography (GC
  • the remaining NCO groups are reacted with the chain extension amine (component A5) in whole or in part.
  • the proportion of the conversion of the remaining NCO groups is referred to as chain extension.
  • Preferred is a chain extension of from 50% to 105%, more preferably from 60 to 95% and most preferably from 65% to 80%. It is assumed that the remaining NCO groups react with water in the later process and thus largely lead to chain extension through urea formation.
  • the process according to the invention is preferably carried out in a stirred reactor.
  • any of the methods known in the art such as emulsifier shear, acetone, prepolymer, mixed, melt emulsified, ketimine, and solid spontaneous dispersing methods, or derivatives thereof can be used to prepare the dispersions of this invention.
  • emulsifier shear emulsifier shear
  • acetone acetone
  • prepolymer emulsifier shear
  • melt emulsified ketimine
  • solid spontaneous dispersing methods or derivatives thereof
  • solid spontaneous dispersing methods or derivatives thereof
  • Suitable solvents are inert to the functional groups present in the process product from the time of addition to the end of the process.
  • Suitable are e.g. solvents used in paint technology, such as hydrocarbons, ketones and esters, e.g. Toluene, xylene, isooctane, acetone, butanone, methyl isobutyl ketone, ethyl acetate, butyl acetate, tetrahydrofuran, N-methylpyrrolidone, dimethylacetamide, dimethylformamide.
  • solvents used in paint technology such as hydrocarbons, ketones and esters, e.g. Toluene, xylene, isooctane, acetone, butanone, methyl isobutyl ketone, ethyl acetate, butyl acetate, tetrahydrofuran, N-methylpyrrolidone, dimethylacetamide, dimethylformamide.
  • novel polyurethanes A) and the dispersions prepared therewith are particularly suitable as binders for coating compositions. Therefore, a further preferred embodiment of the present invention relates to the use of the polyurethane A) according to the invention as a binder in a coating composition.
  • Said coating agent is more preferably a one-component coating agent, i. a coating agent to which no further compound is added which causes crosslinking of individual molecules of the polyurethane A).
  • the coating agent is aqueous.
  • the coating composition according to the invention contains, apart from one or more polyurethanes A) according to the invention, no further binder.
  • the coating composition according to the invention consists of at least one polyurethane A), a siccative C) and at least one further component selected from the group consisting of components B), D) and E).
  • aqueous binders may be used, e.g. Polyacrylate dispersions, polyacrylate emulsions, other alkyd dispersions, polyurethane-polyacrylate dispersions, polyurethane dispersions, aqueous epoxy resins or else crosslinker dispersions, such as e.g. Polyisocyanates which may optionally also have incorporated hydrophilizing groups and contain free or blocked isocyanate groups, polyaziridines or amine crosslinkers, e.g. based on melamine.
  • crosslinker dispersions such as e.g. Polyisocyanates which may optionally also have incorporated hydrophilizing groups and contain free or blocked isocyanate groups, polyaziridines or amine crosslinkers, e.g. based on melamine.
  • siccatives are oxides, salts or complexes of metals such as e.g. Cobalt, vanadium, manganese, copper, iron, zirconium, calcium or zinc.
  • organic solvents may optionally be used in addition to water.
  • examples include various ester alcohols, esters, glycol ethers or Glykolbenzoate such.
  • PnB propylene glycol n-butyl ether
  • DPM dipropylene glycol monomethyl ether
  • DPM 2,2,4-trimethyl-1,3-pentanediol monois
  • UV-absorber and / or HALS stabilizers can be included to increase the weather stability of the cured lacquer layer. Preference is given to a combination of UV absorbers and HALS stabilizers.
  • the former advantageously have an absorption range of at most 390 nm, for example, UV absorbers such as Triphenyltriazintypen (eg Tinuvin ® 400 (Ciba Specialty Chemicals GmbH, Lampertheim, DE)), benzotriazoles (eg Tinuvin® 622 (Ciba Specialty Chemicals GmbH, Lampertheim, DE)) or oxalic acid dianilides (.
  • Suitable HALS stabilizers are available commercially (for example, Tinuvin ® 292 or Tinuvin ® 123 (Ciba Specialty Chemicals GmbH, Lampertheim, DE) or Sanduvor ® 3258 (Clariant, Muttenz, CH)). Preferred amounts are 0.5-2.5 wt .-% based on solid resin.
  • auxiliary agents and additives known in coating technology such as e.g. Pigments including metallic effect pigments, dyes, matting agents, fillers, leveling, wetting and deaerating additives, slip additives, nanoparticles, anti-yellowing additives, thickeners and surface tension reduction additives.
  • Pigments including metallic effect pigments, dyes, matting agents, fillers, leveling, wetting and deaerating additives, slip additives, nanoparticles, anti-yellowing additives, thickeners and surface tension reduction additives.
  • the application of the coating compositions according to the invention to the material to be coated is carried out by the methods commonly known and used in coating technology such as spraying, knife coating, rolling, casting, dipping, spinning, brushing or spraying or by printing techniques such as screen, gravure, flexographic or offset printing as well as by transfer methods.
  • Suitable substrates are, for example, wood, metal, in particular also metal as it is used in the applications of the so-called wire, coil, can or container coating, furthermore plastic in the form of films, in particular ABS, AMMA, ASA, CA, CAB, EP, UF, CF, MF, MPF, PF, PAN, PA, PE, HDPE, LDPE, LLDPE, UHMWPE, PET, PMMA, PP, PS, SB, PUR, PVC, RF, SAN, PBT, PPE, POM, PUR-RIM, SMC, BMC, PP-EPDM, and UP (short names according to DIN 7728T1), paper, leather, textiles, felt, glass, wood-based materials, cork, inorganically bound substrates such as wood and fiber cement boards, electronic assemblies or mineral substrates.
  • plastic in the form of films in particular ABS, AMMA, ASA, CA, CAB, EP, UF, CF, MF, MPF, PF, PAN, PA,
  • substrates that consist of various of the aforementioned materials, or already coated substrates such as vehicles, aircraft or ships and their parts, especially bodies or attachments are painted. It is also possible to apply the coating agent only temporarily to a substrate, then to partially or completely harden it and, if necessary, to remove it again, in order, for example, to remove it. Produce films.
  • the coating compositions of the invention are particularly suitable for coating wood, wood-containing substrates, cork and cellulose fiber-containing substrates, such as paper or Cardboard.
  • the coating compositions according to the invention are particularly suitable for coating wood.
  • venting e.g. contained water or optionally solvents are completely or partially removed.
  • the thermal curing at room temperature but also at elevated temperature preferably at 0 - 160 ° C, preferably at 10 - 60 ° C, particularly preferably at 15 - 35 ° C take place.
  • the applied layer thicknesses are typically between 0.5 and 5000 ⁇ m, preferably between 5 and 1000 ⁇ m, particularly preferably between 15 and 200 ⁇ m. When using solvents, this is removed after application and before curing by the common methods.
  • Another object of the invention are substrates coated with the coating compositions of the invention containing the polyurethane dispersions of the invention.
  • the solids content of the polyurethane dispersion was determined gravimetrically after evaporation of all nonvolatile constituents in accordance with DIN EN ISO 3251.
  • the mean particle size was determined by laser correlation spectroscopy.
  • the flow time was determined in accordance with DIN 53211 using the 4 mm DIN cup.
  • the OH number was determined according to DIN 53240-2.
  • the acid number was determined according to DIN EN ISO 2114.
  • Example 1 aqueous polyurethane dispersion according to the invention
  • the polyurethane dispersions prepared were mixed under shear in the disperser at 1500 revolutions / min successively according to Table 1 with the formulation constituents.
  • the resulting varnish was applied three times with a brush in a thin layer on an oak panel, each about 3 hours ventilated and the first two layers then sanded with sandpaper (P180).
  • the pendulum hardness according to König was tested according to DIN EN ISO 1522.
  • the heel strike resistance was determined by abruptly injuring the film surface with a commercially available repair shoe sole.
  • the shoe sole is clamped in a pendulum-like apparatus, deflected and swung over the coated wooden plate.
  • the degree of damage (after removal of the rubber abrasion) was evaluated on a scale of 1 to 5, where (similar to chemical resistance) 1 means complete destruction of the film and 5 represents a completely undamaged film.
EP15199189.0A 2015-12-10 2015-12-10 Dispersions de polyuréthane séchant par oxydation ayant une résistance particulièrement élevée aux produits chimiques Active EP3178860B1 (fr)

Priority Applications (4)

Application Number Priority Date Filing Date Title
ES15199189T ES2706826T3 (es) 2015-12-10 2015-12-10 Dispersiones de poliuretano de secado oxidativo con una resistencia a productos químicos especialmente alta
EP15199189.0A EP3178860B1 (fr) 2015-12-10 2015-12-10 Dispersions de polyuréthane séchant par oxydation ayant une résistance particulièrement élevée aux produits chimiques
US15/370,066 US10640604B2 (en) 2015-12-10 2016-12-06 Oxidatively drying polyurethane dispersions with particularly high chemical resistance
CN201611273031.XA CN106866931A (zh) 2015-12-10 2016-12-09 具有特别高耐化学性的氧化干燥的聚氨酯分散体

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
EP15199189.0A EP3178860B1 (fr) 2015-12-10 2015-12-10 Dispersions de polyuréthane séchant par oxydation ayant une résistance particulièrement élevée aux produits chimiques

Publications (2)

Publication Number Publication Date
EP3178860A1 true EP3178860A1 (fr) 2017-06-14
EP3178860B1 EP3178860B1 (fr) 2018-11-28

Family

ID=54849469

Family Applications (1)

Application Number Title Priority Date Filing Date
EP15199189.0A Active EP3178860B1 (fr) 2015-12-10 2015-12-10 Dispersions de polyuréthane séchant par oxydation ayant une résistance particulièrement élevée aux produits chimiques

Country Status (4)

Country Link
US (1) US10640604B2 (fr)
EP (1) EP3178860B1 (fr)
CN (1) CN106866931A (fr)
ES (1) ES2706826T3 (fr)

Citations (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2446440A1 (de) 1974-09-28 1976-04-08 Bayer Ag Verfahren zur herstellung von polyurethanen
EP0017199A1 (fr) 1979-03-29 1980-10-15 Textron Inc. Polyuréthanes dispersables dans l'eau et dispersions aqueuses les contenant
US5039732A (en) 1988-12-30 1991-08-13 The Sherwin-Williams Company Water-dispersable air-drying coatings
EP0379007B1 (fr) 1989-01-17 1993-10-06 Bayer Ag Procédé pour la préparation de résines alkyde aqueuses s'oxydant au séchage et leur usage comme peintures ou matières de revêtement aqueuses
JPH06340842A (ja) 1993-05-31 1994-12-13 Dainippon Ink & Chem Inc 水性塗料用樹脂組成物
DE4416336A1 (de) 1994-05-09 1995-11-16 Hoechst Ag Hydrophile Polyurethan-Polyharnstoffe und deren Verwendung als Dispergiermittel für Kunstharze
EP0540985B1 (fr) 1991-11-07 1996-01-03 Bayer Ag Mélanges de polyisocyanates dispersibles dans l'eau
EP0709414A1 (fr) 1994-10-27 1996-05-01 Alberdingk Boley GmbH Utilisation d'huiles de ricin partiellement déshydratées pour la préparation de dispersions aqueuses de plyuréthane et revêtements préparés en utilisant ces dispersions aqueuses de polyuréthane
WO1997019120A1 (fr) 1995-11-21 1997-05-29 Akzo Nobel N.V. Polyurethanne insature dispersible dans l'eau
EP0916647A2 (fr) 1997-11-13 1999-05-19 Bayer Ag Agent hydrophile, procédé pour sa préparation et son utilisation comme agent dispersant pour des dispersions aqueuses de polyuréthane
EP1198487A1 (fr) 1999-07-05 2002-04-24 Bayer Aktiengesellschaft Dispersions polyurethane
WO2002032980A1 (fr) * 2000-10-14 2002-04-25 Avecia B.V. Compositions aqueuses de revetement de polyurethanne
EP0753531B1 (fr) 1995-07-13 2003-03-19 Wolff Walsrode Ag Dispersions aqueuses durcissables par irradiation, leur préparation et utilisation
DE102010009896A1 (de) * 2010-03-02 2011-09-08 Bayer Materialscience Ag Wässrige Polyurethandispersionen

Family Cites Families (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4046729A (en) * 1975-06-02 1977-09-06 Ppg Industries, Inc. Water-reduced urethane coating compositions
DE10215053A1 (de) * 2002-04-05 2003-10-23 Bayer Ag Polyurethan-Dispersionen auf Basis von Fettsäuredialkanolamiden
ATE465220T1 (de) * 2004-10-26 2010-05-15 Lubrizol Advanced Mat Inc Wassergetragene dispersionen öl-modifizierter urethanpolymere
CN100475874C (zh) * 2006-03-10 2009-04-08 广东天银化工实业有限公司 高效氧化自交联型水性聚氨酯分散体及其制备方法
US20070287824A1 (en) * 2006-06-08 2007-12-13 Johnson Mitchell T Waterbased polyurethane floor coating composition
DE102006054237A1 (de) * 2006-11-17 2008-05-21 Bayer Materialscience Ag Polyurethan-modifizierte Alkydharzdispersionen
EP2110395A1 (fr) * 2008-04-18 2009-10-21 Bayer MaterialScience AG Solutions de polyuréthane aqueuses pour systèmes de polyuréthane
ES2444778T3 (es) * 2009-09-17 2014-02-26 Bayer Materialscience Ag Poliuretanoureas hidrófilas basadas en ciclohexanodimetanol
CN102627898B (zh) * 2012-03-28 2014-05-14 湖南福湘涂料化工科技有限公司 一种开放时间较长的水性涂料及其制备方法
EP2746311B1 (fr) * 2012-12-19 2016-09-21 Rohm and Haas Company Revêtement de polyuréthane à deux composants à base d'eau comprenant des polyols rigide alicyclique

Patent Citations (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2446440A1 (de) 1974-09-28 1976-04-08 Bayer Ag Verfahren zur herstellung von polyurethanen
EP0017199A1 (fr) 1979-03-29 1980-10-15 Textron Inc. Polyuréthanes dispersables dans l'eau et dispersions aqueuses les contenant
US5039732A (en) 1988-12-30 1991-08-13 The Sherwin-Williams Company Water-dispersable air-drying coatings
EP0379007B1 (fr) 1989-01-17 1993-10-06 Bayer Ag Procédé pour la préparation de résines alkyde aqueuses s'oxydant au séchage et leur usage comme peintures ou matières de revêtement aqueuses
EP0540985B1 (fr) 1991-11-07 1996-01-03 Bayer Ag Mélanges de polyisocyanates dispersibles dans l'eau
JPH06340842A (ja) 1993-05-31 1994-12-13 Dainippon Ink & Chem Inc 水性塗料用樹脂組成物
DE4416336A1 (de) 1994-05-09 1995-11-16 Hoechst Ag Hydrophile Polyurethan-Polyharnstoffe und deren Verwendung als Dispergiermittel für Kunstharze
EP0709414B1 (fr) 1994-10-27 1999-06-02 Alberdingk Boley GmbH Utilisation d'huiles de ricin partiellement déshydratées pour la préparation de dispersions aqueuses de plyuréthane et revêtements préparés en utilisant ces dispersions aqueuses de polyuréthane
EP0709414A1 (fr) 1994-10-27 1996-05-01 Alberdingk Boley GmbH Utilisation d'huiles de ricin partiellement déshydratées pour la préparation de dispersions aqueuses de plyuréthane et revêtements préparés en utilisant ces dispersions aqueuses de polyuréthane
EP0753531B1 (fr) 1995-07-13 2003-03-19 Wolff Walsrode Ag Dispersions aqueuses durcissables par irradiation, leur préparation et utilisation
WO1997019120A1 (fr) 1995-11-21 1997-05-29 Akzo Nobel N.V. Polyurethanne insature dispersible dans l'eau
EP0916647A2 (fr) 1997-11-13 1999-05-19 Bayer Ag Agent hydrophile, procédé pour sa préparation et son utilisation comme agent dispersant pour des dispersions aqueuses de polyuréthane
EP1198487A1 (fr) 1999-07-05 2002-04-24 Bayer Aktiengesellschaft Dispersions polyurethane
EP1198487B1 (fr) 1999-07-05 2005-12-21 Bayer MaterialScience AG Dispersions polyurethane
WO2002032980A1 (fr) * 2000-10-14 2002-04-25 Avecia B.V. Compositions aqueuses de revetement de polyurethanne
DE102010009896A1 (de) * 2010-03-02 2011-09-08 Bayer Materialscience Ag Wässrige Polyurethandispersionen

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
"Advances in Urethane Science and Technology", vol. 10, 1987, pages: S121FF
D.DIETERICH, PROG. ORG. COATINGS, vol. 9, 1981, pages 281
HOUBEN-WEYL: "Methoden der Organischen Chemie", vol. E20, 1987, GEORG THIEME VERLAG, pages: 1682

Also Published As

Publication number Publication date
ES2706826T3 (es) 2019-04-01
US20170166685A1 (en) 2017-06-15
CN106866931A (zh) 2017-06-20
EP3178860B1 (fr) 2018-11-28
US10640604B2 (en) 2020-05-05

Similar Documents

Publication Publication Date Title
EP2655458B1 (fr) Procédé de préparation de dispersions d'hybrides de polyuréthane-polyacrylate
EP1958974B1 (fr) Dispersions durcissables par uv à base de polysocyanates
DE19715382C1 (de) Wasserdispergierte, strahlenhärtbare Polyurethane
EP2581396B1 (fr) Procédé de fabrication d'uréthane(méth)acrylates pouvant se dissoudre dans l'eau et peu visqueux
DE102006054237A1 (de) Polyurethan-modifizierte Alkydharzdispersionen
AT409134B (de) Oxydativ trocknende polyurethandispersionen
DE102005036654A1 (de) Selbstvernetzende PUR-Dispersionen mit Uretdionstruktur
DE102004051861A1 (de) Verwendung einer wässrigen Dispersion auf Basis eines ungesättigten, amorphen Polyesters auf Basis bestimmter Dicidolisomerer
WO2006089648A1 (fr) Solutions de polyurethane-uree
WO2016071245A1 (fr) Nouvelles dispersions de polyuréthane à base de matières premières renouvelables
EP2963073A1 (fr) Produits de réaction et apprêt en base aqueuse contenant les produits de réaction
EP2840101A1 (fr) Réactif contenant des acides gras dimères et moyen de revêtement contenant le réactif
WO2015189084A1 (fr) Dispersions de polymères contenant des acylmorpholines
WO2007000415A1 (fr) Materiaux de revetement contenant du 2,4'-diisocyanatodiphenylmethane
DE102013108828B4 (de) Wässrige, hydroxylgruppenhaltige Polyurethandispersionen, ein Verfahren zu deren Herstellung und deren Verwendung in Beschichtungsmitteln
AT500555B1 (de) Selbstvernetzende wässrige polyurethandispersionen
WO2006094851A1 (fr) Compositions aqueuses de matieres de revetement destinees a des fonds flexibles
WO2010043374A1 (fr) Laque durcissable au rayonnement actinique ou thermiquement et au rayonnement actinique, résistant aux éraflures et aux intempéries
AT410096B (de) Wasserverdünnbare bindemittel für ''soft-feel''-lacke
EP3505548A1 (fr) Composés polyurées modifiés par un alcoxysilane à base d'un mélange de dialcoxysilanes et de trialcoxysilanes
DE4314252A1 (de) Olefinisch ungesättigte Isocyanate
EP3178860B1 (fr) Dispersions de polyuréthane séchant par oxydation ayant une résistance particulièrement élevée aux produits chimiques
EP3110865B1 (fr) Polymère dans des peintures multicouches donnant des couleurs et/ou des effets
EP3039052B1 (fr) Réactif de polyesterdiol d'acides gras dimères et son utilisation dans des produits de revêtement
WO2016162215A1 (fr) Dispersions polymères contenant de la n-acylpyrrolidine

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

AX Request for extension of the european patent

Extension state: BA ME

17P Request for examination filed

Effective date: 20171214

RBV Designated contracting states (corrected)

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

GRAP Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOSNIGR1

RIC1 Information provided on ipc code assigned before grant

Ipc: C08G 18/10 20060101ALI20180604BHEP

Ipc: C08G 18/12 20060101ALI20180604BHEP

Ipc: C08G 18/67 20060101ALI20180604BHEP

Ipc: C08G 18/75 20060101AFI20180604BHEP

Ipc: C08G 18/08 20060101ALI20180604BHEP

Ipc: C08G 18/32 20060101ALI20180604BHEP

Ipc: C08G 18/34 20060101ALI20180604BHEP

Ipc: C09D 175/14 20060101ALI20180604BHEP

Ipc: C08G 18/36 20060101ALI20180604BHEP

Ipc: C09F 9/00 20060101ALI20180604BHEP

Ipc: C08G 18/24 20060101ALI20180604BHEP

INTG Intention to grant announced

Effective date: 20180626

GRAS Grant fee paid

Free format text: ORIGINAL CODE: EPIDOSNIGR3

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

REG Reference to a national code

Ref country code: CH

Ref legal event code: EP

REG Reference to a national code

Ref country code: AT

Ref legal event code: REF

Ref document number: 1070134

Country of ref document: AT

Kind code of ref document: T

Effective date: 20181215

REG Reference to a national code

Ref country code: DE

Ref legal event code: R096

Ref document number: 502015006982

Country of ref document: DE

REG Reference to a national code

Ref country code: IE

Ref legal event code: FG4D

Free format text: LANGUAGE OF EP DOCUMENT: GERMAN

REG Reference to a national code

Ref country code: NL

Ref legal event code: FP

REG Reference to a national code

Ref country code: SE

Ref legal event code: TRGR

REG Reference to a national code

Ref country code: ES

Ref legal event code: FG2A

Ref document number: 2706826

Country of ref document: ES

Kind code of ref document: T3

Effective date: 20190401

REG Reference to a national code

Ref country code: LT

Ref legal event code: MG4D

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: BG

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20190228

Ref country code: NO

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20190228

Ref country code: IS

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20190328

Ref country code: HR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20181128

Ref country code: LT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20181128

Ref country code: LV

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20181128

Ref country code: FI

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20181128

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20190301

Ref country code: AL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20181128

Ref country code: RS

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20181128

Ref country code: PT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20190328

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: PL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20181128

Ref country code: DK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20181128

Ref country code: CZ

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20181128

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

REG Reference to a national code

Ref country code: DE

Ref legal event code: R097

Ref document number: 502015006982

Country of ref document: DE

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: MC

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20181128

Ref country code: LU

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20181210

Ref country code: SK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20181128

Ref country code: RO

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20181128

Ref country code: EE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20181128

Ref country code: SM

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20181128

REG Reference to a national code

Ref country code: IE

Ref legal event code: MM4A

PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SI

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20181128

Ref country code: IE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20181210

26N No opposition filed

Effective date: 20190829

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: CH

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20181231

Ref country code: LI

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20181231

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: MT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20181128

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: TR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20181128

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: GB

Payment date: 20191206

Year of fee payment: 5

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: CY

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20181128

Ref country code: HU

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT; INVALID AB INITIO

Effective date: 20151210

Ref country code: MK

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20181128

GBPC Gb: european patent ceased through non-payment of renewal fee

Effective date: 20201210

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GB

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20201210

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: SE

Payment date: 20211126

Year of fee payment: 7

Ref country code: FR

Payment date: 20211125

Year of fee payment: 7

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: NL

Payment date: 20211203

Year of fee payment: 7

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: ES

Payment date: 20230110

Year of fee payment: 8

REG Reference to a national code

Ref country code: SE

Ref legal event code: EUG

REG Reference to a national code

Ref country code: NL

Ref legal event code: MM

Effective date: 20230101

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: NL

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20230101

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20221211

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: FR

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20221231

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: IT

Payment date: 20231128

Year of fee payment: 9

Ref country code: DE

Payment date: 20231121

Year of fee payment: 9

Ref country code: AT

Payment date: 20231127

Year of fee payment: 9

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: BE

Payment date: 20231129

Year of fee payment: 9

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: ES

Payment date: 20240115

Year of fee payment: 9